Plastics articles such as bottles with visual effect

ABSTRACT

Plastic articles, and in particular polycarbonate articles, provide an appealing aesthetic look in the form of a colored glow at locations defined by cuts and/or protrusions in the surface of the article as a result of incorportation of a photoluminescent material in the polycarbonate from which the article is formed. The cuts and/or protrusions define a graphic image, for example one or more letters (i.e., an initial or name), an abstract design, a drawing or a trademark or logo. Ambient light entering the plastic body results in luminescence from the photoluminescent material which is conducted as a result of internal reflectance within the plastic body to the edges of the cuts in the bodies surface.

BACKGROUND OF INVENTION

[0001] This application relates to plastic articles such as bottleswhich provide a visual effect in the form of an aesthetic colored glowat locations defined by cuts or protrusions in the surface of thearticle.

[0002] Plastics, including polycarbonate, are commonly employed in themanufacture of bottles, particularly reusable water bottles, and otherarticles. These articles may be substantially colorless or they may beprepared in decorative colors.

SUMMARY OF INVENTION

[0003] The present invention provides plastic articles, and inparticular polycarbonate articles, that provide an appealing aestheticlook in the form of a colored glow at locations defined by cuts and/orprotrusions in the surface of the article as a result of incorporationof a photoluminescent material in the polycarbonate from which thearticle is formed. The cuts or protrusions define a graphic image, forexample one or more letters or numbers (i.e., an initial or name), anabstract design, a drawing or a trademark or logo. Ambient lightentering the plastic body results in luminescence from thephotoluminescent material which is conducted as a result of internalreflectance within the plastic body to the edges of the cuts in thebodies surface.

BRIEF DESCRIPTION OF DRAWINGS

[0004] FIGS. 1A-C show the shape of cuts that can be used to producegraphic images on an article in accordance with the invention;

[0005]FIG. 2 shows a combination of cuts and protrusions that can beused to produce graphic images on an article in accordance with theinvention;

[0006]FIGS. 3A and B shows articles in accordance with the inventionwith annular bodies;

[0007]FIG. 4 shows an article in accordance with the invention with aflat surface; and

[0008]FIG. 5 shows an article in accordance with the invention with anirregular surface.

DETAILED DESCRIPTION

[0009] This application relates to plastic articles that are formed froma combination of a transparent plastic a photoluminescent material.These articles provide an aesthetic visual effect in the form of acolored glow at cuts or protrusions formed in the surface of thearticle.

[0010] In general, the articles of the invention may be any utilitarianarticle which may be formed from molded plastic and in which it would bedesirable to have a luminescent image provided. The exception is lensesand lamp bezels for use in combination with a specific light source, forexample in automotive headlamps. Because lenses and bezels are intendedto be used with specific light sources (for example High intensitydischarge automotive headlamps) rather than ambient light, they are thesubject of a separate application (U.S. Provisional Application SerialNo. 60/370,790, filed Apr. 5, 2002 and a U.S. utility application Ser.No. 10/063791, filed concurrently herewith, both of which areincorporated herein by reference).

[0011] As used in the specification and claims of this application, theterm “graphic image” refers to any image which may be desired on thearticle, or example one or more letters or numbers (i.e., an initial orname), an abstract design, a drawing, or a trademark or logo. Theluminescent graphic image formed by the cuts and/or protrusions maycomplement a non-luminescent image that is incorporated into thearticle. Thus, for example, the luminescent image on a cover sheet for aphotograph might provide a halo or a mustache to be viewed incombination with a photograph placed under the cover.

[0012] The articles of the present invention may be formed from anytransparent or translucent thermoplastic material that has an index ofrefraction sufficiently different from air to produce a degree ofinternal reflectance such that an amount of light sufficient to producea luminescent visual effect is conducted within the plastic material toa cut in or protrusion from the surface. Generally at least 10% of thelight emitted by photoluminescence is conducted through the interior ofthe article to the edges of the cut or protrusion, preferably at least30%. To achieve this level of internal reflectance, it is desirable thatthe thermoplastics employed have an index of refraction of at least 1.4at room temperature. It is also desirable that the thermoplastics havegood light transmission and a low haze. Good light transmission isdefined here as a minimum of 60% and good haze as a haze value of lessthan 10% as measured per ASTM D1003 at 3 mm thickness. Amorphousthermoplastic materials are therefore preferred but somesemi-crystalline materials with less than 30% crystallinity ratio may beemployed. Thermoplastics which have this characteristic include, withoutlimitation, polycarbonate (PC), polyethylene terephtalate (PET),polymethyl methacrylate (PMMA), polystyrene (PS), polyvinyl chloride(PVC), clarified polyolefins, poyetherimide (PEI), polyphenylene ether(PPE), amorphous aromatic polyamides like PA 6-3T, and polysulfones.Preferred plastics are polycarbonates, which combine high indices ofrefraction of around 1.58, light transmission of about 87% and haze ofabout 1% at 3 mm thickness. Polycarbonate can be easily blow molded toform bottles or similar containers with great impact resistance whichare therefore reusable. It is also FDA approved which is an absoluterequirement for all containers used in food packaging or food service.Due to its elevated glass transition temperature, it can be fullysterilized at high temperature without irreversibly loosing itsmechanical properties conversely to other thermoplastics like PVC orPET.

[0013] When cuts are used to form the graphic image, the cut should havesufficient depth to produce a substantial surface for escape of emittedlight, but should not be so deep as to impair the structural integrityof the article. Thus, the permitted depth will depend of the thicknessof the article, the purpose for which it is to be used, and the natureof the plastic. For many purposes and materials, however, cuts on theorder of 0.5 to 3 mm in depth are appropriate. The cuts may be made invarious shapes. For example, as depicted in FIG. 1A, the cut may have arectangular bottom. In this embodiment, it may be desirable to providetexturing as represented by the dashed line 11 at the bottom of the cutto permit emission from this surface and increase the magnitude of thevisual effect. Non-textured sides for the cut are preferred in order tocreate a homogenous light emission in this part of the cut. FIG. 1Bshows a cut with a V-shaped bottom. FIG. 1C shows a cut with atrapezoidal shape. Again, the bottom of the cut may be textured, ifdesired, to increase the intensity of the visual effect. The bottom ofthe cut can also be rounded in order to facilitate tool (i.e. mold)manufacture, allow easier filling of the tool by the moltenthermoplastic during blow-molding operation, and reduce local stress inthe article.

[0014] When protrusions are used to form the graphic image, theprotrusions may be rectangular, V-shaped, trapezoidal, and may haverounded edges if desired. Similar to the cuts, any top surface of theprotrusion may be textured to increase the light intensity escaping fromthe surface, and thus the visual effect. The protrusion should have aheight above the main surface of the article sufficient to allow escapeof light in observable amounts through the sides surfaces of theprotrusion. In general, it will be desirable to have protrusions of atleast 0.5 mm, for example 1 to 5 mm, consistent with the size andpurpose of the article.

[0015] Articles in accordance with the invention may have a combinationof protrusions and cuts. Thus, as shown in FIG. 2, a trapezoidalprotrusion 21, which is elevated relative to the main article surface23, is positioned adjacent to a trapezoidal cut 22, which is inset belowmain article surface 23. The protrusion 21 and the cut 22 are shown ascontiguous features, but there could also be an intervening portion ofthe main article surface. By combining cuts and protrusions of differentshapes and surface areas, visual effects which combine regions ofdifferent intensities can be achieved.

[0016] The articles of the invention are suitably formed by moldingprocesses conventionally employed in the formation of plastic articles.For example, the articles may be formed by blow-molding, injectionmolding, thermoforming, or sheet/film extrusion. In some instances, thecuts can be achieved after molding of the article using a hot stampingprocess or a laser beam.

[0017] In one embodiment of the present invention, the articles comprisean annular body, for example a right cylinder (circular, elliptical orother closed rounded shape), having a contiguous bottom and a contiguoustop. In the case of a water bottle of the type shown in FIG. 3A, thebottom 31 is substantially flat, while the top has a neck 32 forreceiving a cap and shoulders 33 extending outwards to join with thesides of the annular body 34. Many larger water bottles, such as 5gallon water bottles used in water coolers do not have a threaded neckbecause they would have compatibility problems with some water coolers.The cap is usually snapped on and there is a removable seal thatprotects the water in the bottle from contamination. Other bottle types,such as water bottles used for hiking or biking, or beverage bottles,may have threaded necks. Other shapes for the bottom and top, and wellas non-circular and angled cylinders, may also be used. In accordancewith the invention, cuts or protrusions are formed in the surface of theannular body, the bottom, the top, or some combination thereof to form agraphic image 35. If desired, an integral handle 36 may be formed in themolding process.

[0018] In another embodiment of the invention, as depicted in FIG. 3B,the article comprises an annular body member 34 with a bottom 31 but notop. Depending on size, such an article could be used as a storagereceptacle, laundry hamper or a vase.

[0019] In a further embodiment of the invention, the article comprises aflat or flattened disc or rectangular body. Articles with thisconfiguration include but are not limited to key fobs; one or more sidesof a box, for example jewelry boxes or lunch boxes; panes for coveringpictures; flat panels which can be used in chandeliers or wind chimes,office and desk accessories, including clip boards, CD cases, rulers,and trays; and window ornaments. For example, FIG. 4 shows a pictureholder formed from molded plastic which has a border 45 cut into theflat surface 44.

[0020] In a further embodiment of the invention the molded plasticcomponent has an irregular three-dimensional shape with cuts formed inthe surface thereof to produce a pattern of luminescence thatcomplements the three dimensional shape. Such articles include but arenot limited to jewelry, beads, buttons, toys (for example pin wheels ormolded characters), picture frames, eye glasses (lens or frames), penbarrels, telephones or telephone covers. FIG. 5 shows a bead inaccordance with the invention. Cuts 55 are formed in the surface of thebead 51, defining lines along which the visual effect will occur.

[0021] The articles of the present invention comprise a molded bodyhaving a major outer surface and edge surfaces formed by theintroduction of cuts or protrusions defining a graphic image. Thearticles are formed from a high-refractive index plastic, such aspolycarbonate, and a photoluminescent material. Light which includeslight of a wavelength within the excitation spectrum of thephotoluminescent dye is partially absorbed and partially transmitted.The absorbed light is at least partially (depending on the quantum yieldof the luminescence) emitted as light of a higher wavelength (as aresult of a Stokes shift) and is conducted to a substantial extent tothe edge surfaces of the article (those formed by cuts, and those whichare inherent in the shape of the article) thereby creating a coloredvisual effect at the edges. As used in the specification and claims ofthis application, the term “substantial extent” means in an amounteffective to create an observable visual effect.

[0022] As used in the specification and claims of this application, theterm “photoluminescent material” refers to any substance that exhibitsphotoluminescence in response to excitation energy provided by ambientlight (sunlight, room light and other artificial light sources),including without limitation organic compounds that solubilize in theplastic polymer matrix during the compounding operation, organicnanoparticle dyes (also known as “nano-colorants”) and inorganicphotoluminescent materials, including nanoparticles. Photoluminescenceoccurs when a substance absorbs radiation of a certain wavelength andre-emits photons, generally of a different and longer wavelength. When aphotoluminescent molecule absorbs light, electrons are excited to ahigher “excited” energy state. The molecule then loses part of itsexcess of energy by collisions and internal energy conversions and fallsto the lowest vibrational level of the excited state. From this level,the molecule can return to any of the vibrational levels of the groundstate, emitting its energy in the form of photoluminescence.Photoluminescence is a generic term which encompasses both fluorescenceand phosphorescence. In the present invention, the photoluminescentmaterials are preferably organic fluorescent dyes because of the higherquantum yield associated with fluorescence as opposed to other types ofphotoluminescent processes. Preferably, the organic fluorescent dye isselected to have a quantum yield of fluorescence of at least 0.7, morepreferably at least 0.8 and most preferably at least 0.9 Typically, theemission by fluorescence is an extremely brief phenomenon lastinggenerally between 10⁻⁴ and 10⁻⁹ seconds.

[0023] Specific non-limiting examples of fluorescent dyes that may beused in the articles of the invention are perylene derivatives,anthracene derivatives, indigoid and thioindigoid derivatives, imidazolederivatives, naphtalimide derivatives, xanthenes, thioxanthenes,coumarins, rhodamines, or(2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene) and all theirderivatives. Non-fluorescent dyes may be selected from but are notlimited to the following families: azo dyes, methine dyes, pyrazolones,quinophtalones, perinones, anthraquinones, phtalocyanines and all theirderivatives. In general, very low loadings of dyes, for example lessthan 1.0% are used to create the effect described in this invention. Incertain cases, it may be desired to have a final object with the effectof this invention but with almost no visible color (for example a“clear” water bottle). In these cases, the fluorescent dye loading canbe extremely low, sometimes as low as 0.0001%. Except for theblue/violet colors and maybe some greens, the fluorescent dye loading toretain the “clear” appearance is usually lower than 0.0005% by weight,for example from 0.0001% to 0.0003% by weight, which is enough togenerate a very noticeable visual effect at the edges of the article. Inthe blue/violet colors, the fluorescent dye loading is significantlyhigher due to the fact that most of its absorption is located in the UVrange. Typically, the fluorescent dye loading in this case is between0.005% to 0.5% by weight, with 0.01% to 0.2% being preferred and 0.03%to 0.1% being most preferred.

[0024] Nano-colorants can be obtained by various methods and usuallycombine the advantages of both dyes and pigments. Their light fastnesscompared to the corresponding dye molecule is usually greatly improved.Since their particle size is in general less than 100 nanometers,preferably less than 50 nm, and more preferably less than 10 nm, they donot scatter light conversely to most pigments used to color plastics.Nano-colorants can be obtained by various methods. For example, dyemolecules can be converted to nano-colorants by adsorption on anano-clay particle (with or without creating a chemical bond between thenano-clay and the dye) or by nano-encapsulation in a polymer matrix(usually acrylic polymer). Note that the encapsulation method usuallyinvolves emulsion polymerization in order to form sphericalnano-particles of polymer in which the dye is dispersed. Nano-colorantscan be fluorescent if the dye molecule (or the inorganic compound) usedto prepare the nano-colorant is fluorescent. Specific non-limitingexamples of fluorescent dyes that may be employed to form nano-colorantsused in the articles of the invention are perylene derivatives,anthracene derivatives, indigoid and thioindigoid derivatives, imidazolederivatives, naphtalimide derivatives, xanthenes, thioxanthenes,coumarins, rhodamines, or(2,5-bis[5-tert-butyl-2-benzoxazolyl]-thiophene) and all theirderivatives

[0025] Inorganic nano-particles may also be used as nano-colorantsalthough their extinction coefficient is usually fairly low. Examples offluorescent inorganic nano-particles include, but are not limited to,lanthanide complexes and chelates (for instance Europium chelates). Notethat some of these inorganic nano-colorant may exhibit a larger Stokesshift than organic fluorescent colorant, i.e. emit light at a muchlonger wavelength than the excitation wavelength.

[0026] When the article is formed from polycarbonate, the polycarbonatecomponent suitably includes compositions having structural units of theformula (I) and a degree of polymerization of at least 4:

[0027] in which at least about 60 percent of the total number of R¹groups are aromatic organic radicals and the balance thereof arealiphatic, alicyclic, or aromatic radicals. Preferably, R¹ is anaromatic organic radical and, more preferably, a radical of the formula(II):

A¹-Y¹-A²⁻  (II)

[0028] wherein each of A¹ and A² is a monocyclic divalent aryl radicaland Y¹ is a bridging radical having zero, one, or two atoms whichseparate A¹ from A². In an exemplary embodiment, one atom separates A¹from A². Illustrative, non-limiting examples of radicals of this typeare —O—, —S—, —S(O)—, —S(O₂)—, —C(O)—, methylene, cyclohexyl-methylene,2ethylidene, isopropylidene, neopentylidene, cyclohexylidene,cyclopentadecylidene, cyclododecylidene, adamantylidene, and the like.In another embodiment, zero atoms separate A¹ from A², with anillustrative example being biphenol (OH-benzene-benzene-OH). Thebridging radical Y can be a hydrocarbon group or a saturated hydrocarbongroup such as methylene, cyclohexylidene or isopropylidene.

[0029] Polycarbonates can be produced by the reaction of dihydroxycompounds in which only one atom separates A¹ and A². As used herein,the term “dihydroxy compound” includes, for example, bisphenol compoundshaving general formula (III) as follows:

[0030] wherein R^(a) and R^(b) each independently represent hydrogen, ahalogen atom, or a monovalent hydrocarbon group; p and q are eachindependently integers from 0 to 4; and X^(a) represents one of thegroups of formula (IV):

[0031] wherein R^(c) and R^(d) each independently represent a hydrogenatom or a monovalent linear or cyclic hydrocarbon group, and R^(e) is adivalent hydrocarbon group.

[0032] Some illustrative, non-limiting examples of suitable dihydroxycompounds include dihydric phenols and the dihydroxy-substitutedaromatic hydrocarbons such as those disclosed by name or formula(generic or specific) in U.S. Pat. No. 4,217,438. A nonexclusive list ofspecific examples of the types of bisphenol compounds that may berepresented by formula (III) includes the following:1,1-bis(4-hydroxyphenyl)methane; 1,1-bis(4-hydroxyphenyl)ethane;2,2-bis(4-hydroxyphenyl)propane (hereinafter “bisphenol A” or “BPA”);2,2-bis(4-hydroxyphenyl)butane; 2,2-bis(4-hydroxyphenyl)octane; 1,1-bis(4-hydroxyphenyl)propane; 1,1-bis(4-hydroxyphenyl)n-butane;bis(4-hydroxyphenyl)phenylmethane;2,2-bis(4-hydroxy-1-methylphenyl)propane;1,1-bis(4-hydroxy-t-butylphenyl)propane; bis(hydroxyaryl)alkanes such as2,2-bis(4-hydroxy-3-bromophenyl)propane;1,1-bis(4-hydroxyphenyl)cyclopentane; 4,4″-biphenol; andbis(hydroxyaryl)cycloalkanes such as1,1-bis(4-hydroxyphenyl)cyclohexane; and the like as well ascombinations comprising at least one of the foregoing bisphenolcompound.

[0033] It is also possible to employ polycarbonates resulting from thepolymerization of two or more different dihydric phenols or a copolymerof a dihydric phenol with a glycol or with a hydroxy- or acid-terminatedpolyester or with a dibasic acid or with a hydroxy acid or with analiphatic diacid in the event a carbonate copolymer rather than ahomopolymer is desired for use. Generally, useful aliphatic diacids haveabout 2 to about 40 carbons. A preferred aliphatic diacid isdodecandioic acid.

[0034] The polycarbonate component may also include various additivesordinarily incorporated in resin compositions of this type. Suchadditives are, for example, fillers or reinforcing agents; heatstabilizers; antioxidants; light stabilizers; plasticizers; antistaticagents; mold releasing agents; additional resins; and blowing agents.Combinations of any of the foregoing additives may be used. Suchadditives may be mixed at a suitable time during the mixing of thecomponents for forming the composition.

[0035] When the article is formed by injection molding of apolycarbonate resin composition, the polycarbonate formulation issuitably compounded in an extruder in order to provide appropriatemixing of the composition. Although the use of a single-screw extruderis conceivable, a twin-screw extruder is usually preferred to optimizethe mixing and reduce the likelihood of creating scattering particles inthe final product or simply avoid potential streaking issues that maystem from undissolved high-melting point colorants such as some perylenederivatives (melting point around 300° C.). Although the polycarbonatecomposition is generally light stabilized and may be coated with a UVabsorptive coating, it is important to use dyes that combine improvedlight fastness. Good examples of fluorescent dyes with an improved lightfastness are the perylene derivatives like the Lumogen Orange F-240,Lumogen Red F-300 and Lumogen Yellow F-083 supplied by BASF. It is alsopossible to further improve light stability by using nano-colorants.When the desired visual effect is of a blue or violet color and theapplication requires outdoor light stability for an extended period oftime, the use of blue/violet fluorescent nano-colorants should beconsidered.

[0036] In order to better control the extremely low amount of dyesintroduced in the formulation and therefore have a better color controlof the article, the use of volumetric or gravimetric feeders is highlyrecommended. The feeders can either feed a letdown of the concentrate inpolycarbonate resin powder (preferably milled powder) or feed an alreadycompounded (extruded) color masterbatch in a pellet form. The colorantloading in the letdown or the concentration of the masterbatches dependson the feeder capability, and especially the feeding rate. In general,powder letdown vary between 10:1 and 10,000:1 ratios of colorant (i.e.dye) to powder. Dye mixtures can also be used in a letdown form and fedfrom a single feeder although it is not the most preferred method. Poorcolor control may potentially result in articles that would not besuitable for an article application, i.e. beam color or light output notbeing compliant with a defined standard.

[0037] Articles like water bottles are generally made using ablow-molding process from a colorless or colored thermoplastic resin.The main requirement for the resin is its melt strength. For instance,when a blow-molding grade polycarbonate is used, the melt flow index ofthe resin is typically between 1.5 and 3 grams per 10 minutes asmeasured per ASTM 1238 (conditions: 300° C./1.2 kg/1″ orifice).Combination of melt strength and mechanical properties like flexuralmodulus, tensile strength and impact resistance makes polycarbonate thematerial of choice in blow-molding applications especially when objectsexhibiting the edge glow visual effect are needed. Materials with poormelt strength will yield articles with poor mechanical resistance. As acomparison, intricate shapes like water bottles with handles or objectswith deep cuts or sharp protrusions can be blow molded usingpolycarbonate and still retain their physical properties. Typically,blow-molding grades of polycarbonates contain at least 50% of branchedpolycarbonate resin in order to achieve the optimum melt flow strength.Branched polycarbonate has an average molecular weight (Mw) usuallycomprised between 36,000 and 40,000 with a preferred value of about38,000 as measured by gel permeation chromatography. With blow-moldingpolycarbonate grades, it is possible to obtain articles like waterbottles with thin walls (for example 1 mm) and an outstanding impactresistance. When submitted to a drop test from a height of 15 feet, a5-gallon polycarbonate bottle filled with water is totally unharmedwhereas PVC-based or PET-based bottles explode or crack.

[0038] When the graphic image is defined by protrusions these are formedin the course of the molding process. When cuts are employed, they maybe formed during the molding process or in a separate cut-forming stepafter molding is complete. The latter choice is more suited tocustomization of articles in smaller batches.

[0039] Polycarbonate formulations (A) to (G) described below in example1 have been defined to illustrate the ability to create a broad paletteof visual effect color for articles in accordance with the invention. Atwin-screw extruder has been used for the compounding step with standardLexan® LS-2 polycarbonate extrusion conditions. Color chips (5.08cm×7.62 cm×3.2 mm) were molded for each formulation and colorcoordinates were measured on the chips in transmission mode using aMacBeth 7000A spectrophotometer selecting illuminant C and a 2 degreeobserver.

[0040] Polycarbonate formulations (H), (I) and 0) described below inexample 2 have been defined to illustrate the ability to create materialsuitable for blow molding of a water bottle similar to the one presentedin FIG. 3A and exhibiting the visual effect presented in this invention.

EXAMPLES

[0041] The invention will now be further described with reference to thefollowing, non-limiting examples.

Example 1

[0042] A polycarbonate resin composition (A) was prepared by mixing:

[0043] 65 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 29,900

[0044] 35 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0045] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0046] 0.27 parts of pentaerythritol tetrastearate

[0047] 0.27 parts of2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol

[0048] 0.00015 parts of a yellow perylene derivative (BASF LumogenYellow F-083)

[0049] 0.0001 parts of a red perylene derivative (BASF Lumogen RedF-300).

[0050] A polycarbonate resin composition (B) was prepared by mixing:

[0051] 65 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 29,900

[0052] 35 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0053] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0054] 0.27 parts of pentaerythritol tetrastearate

[0055] 0.27 parts of2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol

[0056] 0.00015 parts of a yellow perylene derivative (BASF LumogenYellow F-083)

[0057] 0.000075 parts of C.I. Pigment Blue 60 (BASF Heliogen BlueK6330).

[0058] A polycarbonate resin composition (C) was prepared by mixing:

[0059] 65 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 29,900

[0060] 35 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0061] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0062] 0.27 parts of pentaerythritol tetrastearate

[0063] 0.27 parts of2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol

[0064] 0.01 parts of a naphtalimide derivative (BASF Lumogen VioletF-570)-0.0001 parts of C.I. Pigment Blue 60 (BASF Heliogen Blue K6330)

[0065] 0.00005 parts of C.I. Solvent Violet 36 (Bayer Macrolex Violet3R).

[0066] A polycarbonate resin composition (D) was prepared by mixing:

[0067] 65 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 29,900

[0068] 35 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0069] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0070] 0.27 parts of pentaerythritol tetrastearate

[0071] 0.27 parts of2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol

[0072] 0.05 parts of 2,5-bis(5′-tert-butyl-2-benzoxazolyl)thiophene(Ciba Uvitex OB)

[0073] 0.0001 parts of C.I. Pigment Blue 60 (BASF Heliogen Blue K6330)

[0074] 0.00005 parts of C.I. Solvent Violet 36 (Bayer Macrolex Violet3R).

[0075] A polycarbonate resin composition (E) was prepared by mixing:

[0076] 65 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 29,900

[0077] 35 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0078] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0079] 0.27 parts of pentaerythritol tetrastearate

[0080] 0.27 parts of2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol

[0081] 0.00014 parts of a red perylene derivative (BASF Lumogen YellowF-300).

[0082] A polycarbonate resin composition (F) was prepared by mixing:

[0083] 65 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 29,900

[0084] 35 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0085] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0086] 0.27 parts of pentaerythritol tetrastearate

[0087] 0.27 parts of2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol

[0088] 0.0002 parts of an orange perylene derivative (BASF LumogenOrange F-240).

[0089] A polycarbonate resin composition (G) was prepared by mixing:

[0090] 65 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 29,900

[0091] 35 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0092] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0093] 0.27 parts of pentaerythritol tetrastearate

[0094] 0.27 parts of2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol

[0095] 0.00026 parts of a yellow perylene derivative (BASF LumogenYellow F-083)

[0096] 0.00014 parts of a red perylene derivative (BASF Lumogen RedF-300)

[0097] 0.00003 parts of an orange perylene derivative (BASF LumogenOrange F-240)

[0098] 0.001 parts of 2,5-bis(5′-tert-butyl-2-benzoxazolyl)thiophene(Ciba Uvitex OB).

[0099] The color coordinates and the edge color are summarized inTable 1. This provides a clear illustration of the ability to createvarious visual effect colors with a total visible light transmission (Y)greater than about 87% at 3.2 mm thickness. TABLE 1 Visual effectFormulation Y x Y L* a* B* color A 87.77 0.3170 0.3253 95.06 −1.04 4.58Orange B 88.75 0.3150 0.3257 95.48 −2.23 4.40 Green C 87.70 0.30870.3157 95.04 −0.49 −0.41 Blue # 1 D 87.85 0.3105 0.3202 95.10 −1.82 1.60Blue # 2 E 87.59 0.3121 0.3166 94.99 0.8 0.51 Red/Pink F 88.17 0.31630.3166 95.24 2.97 1.25 Yellow G 86.99 0.3207 0.3292 94.75 −1.06 6.64Orange/ Amber

Example 2

[0100] A polycarbonate resin composition (H) was prepared by mixing:

[0101] 70 parts of branched polycarbonate resin with an averagemolecular weight (M_(W)) of 37,700

[0102] 30 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0103] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0104] 0.05 parts of 2,5-bis(5′-tert-butyl-2-benzoxazolyl)thiophene(Ciba Uvitex OB)

[0105] 0.0025 parts of C.I. Solvent Blue 97 (Bayer Macrolex Blue RR).

[0106] After compounding (extrusion), resin composition (H) was blowmolded to form a water bottle with a blue visual effect.

[0107] A polycarbonate resin composition (I) was prepared by mixing:

[0108] 70 parts of branched polycarbonate resin with an averagemolecular weight (M_(W)) of 37,700

[0109] 30 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0110] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0111] 0.05 parts of 2,5-bis(5′-tert-butyl-2-benzoxazolyl)thiophene(Ciba Uvitex OB)

[0112] 0.00015 parts of C.I. Solvent Violet 36 (Bayer Macrolex Violet3R)

[0113] 0.004 parts of C.I. Solvent Violet 36 (Bayer Macrolex Violet B)

[0114] 0.00035 parts of C.I. Solvent Blue 97 (Bayer Macrolex Blue RR).

[0115] After compounding (extrusion), resin composition (I) was blowmolded to form a water bottle with a violet visual effect.

[0116] A polycarbonate resin composition (J) was prepared by mixing:

[0117] 70 parts of branched polycarbonate resin with an averagemolecular weight (M_(W)) of 37,700

[0118] 30 parts of poly(bisphenol-A carbonate) with an average molecularweight (M_(W)) of 21,900

[0119] 0.06 parts of tris(2,4-di-tert-butylphenyl)phosphite

[0120] 0.015 parts of C.I. Solvent Yellow 98 (Clariant), a yellowxanthene fluorescent dye

[0121] 0.00006 parts of C.I. Vat Red 41 (Clariant), a red thioindigoidfluorescent dye.

[0122] After compounding (extrusion), resin composition (J) was blowmolded to form a water bottle with a yellow visual effect.

1. An article comprising a molded body formed from a plastic compositioncomprising a plastic having an index of refraction of at least 1.4 and aphotoluminescent material, wherein the article has a graphic imageformed as cuts or protrusions, or both, on a surface thereof to providea luminescent visual effect in the shape of the graphic image, with theproviso that the article is not a lamp lens or lamp bezel.
 2. Thearticle of claim 1, wherein the photoluminescent material is an organicfluorescent dye.
 3. The article of claim 2, wherein the fluorescent dyeis included at a concentration of 1% or less by weight of the plastic.4. The article of claim 3, wherein the fluorescent dye provides a blueor violet visual effect and the fluorescent dye is included at aconcentration of 0.5 to 0.001% by weight.
 5. The article of claim 4,wherein the fluorescent dye is included at a concentration of 0.3 to0.1% by weight.
 6. The article of claim 4, wherein the fluorescent dyeis included at a concentration of 0.1% to 0.005% by weight.
 7. Thearticle of claim 3, wherein the fluorescent dye provides a red, orangeor green visual effect and the fluorescent dye is included at aconcentration of less than 0.0005% by weight.
 8. The article of claim 7,wherein the fluorescent dye is included at a concentration of 0.0001% to0.0003% by weight.
 9. The article of claim 2, wherein the fluorescentdye is selected from the group consisting of perylene derivatives,anthracene derivatives, indigoid and thioindigoid derivatives, imidazolederivatives, naphtalimide derivatives, xanthenes, thioxanthenes,coumarins, rhodamines, (2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene)and derivatives thereof.
 10. The article of claim 9, wherein thefluorescent dye is included at a concentration of 1% or less by weightof the plastic.
 11. The article of claim 2, wherein the fluorescent dyehas a quantum yield of 0.7 or greater.
 12. The article of claim 11,wherein the fluorescent dye has a quantum yield of 0.9 or greater. 13.The article of claim 2, wherein the graphic images is formed from cutshaving a depth of from 0.5 to 3 mm or protrusions having a height offrom 0.5 to 5 mm or combinations thereof.
 14. The article of claim 1,wherein the plastic is polycarbonate.
 15. The article of claim 14,wherein the photoluminescent material is an organic fluorescent dye. 16.The article of claim 15, wherein the fluorescent dye is included at aconcentration of 1% or less by weight of the polycarbonate.
 17. Thearticle of claim 16, wherein the fluorescent dye provides a blue orviolet visual effect and the fluorescent dye is included at aconcentration of 0.5 to 0.001% by weight.
 18. The article of claim 17,wherein the fluorescent dye is included at a concentration of 0.3 to0.1% by weight.
 19. The article of claim 17, wherein the fluorescent dyeis included at a concentration of 0.1 to 0.005% by weight.
 20. Thearticle of claim 16, wherein the fluorescent dye provides a red, orangeor green visual effect and the fluorescent dye is included at aconcentration of less than 0.0005% by weight.
 21. The article of claim20, wherein the fluorescent dye is included at a concentration of0.0001% to 0.0003% by weight.
 22. The article of claim 15, wherein thefluorescent dye is selected from the group consisting of perylenederivatives, anthracene derivatives, indigoid and thioindigoidderivatives, imidazole derivatives, naphtalimide derivatives, xanthenes,thioxanthenes, coumarins, rhodamines,(2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene) and derivatives thereof.23. The article of claim 22, wherein the fluorescent dye is included ata concentration of 1% or less by weight of the polycarbonate.
 24. Thearticle of claim 1, wherein the molded body has a substantially annularbody portion.
 25. The article of claim 24, wherein the photoluminescentmaterial is a fluorescent dye.
 26. The article of claim 25, wherein thefluorescent dye is selected from the group consisting of perylenederivatives, anthracene derivatives, indigoid and thioindigoidderivatives, imidazole derivatives, naphtalimide derivatives, xanthenes,thioxanthenes, coumarins, rhodamines,(2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene) and derivatives thereof.27. The article of claim 26, wherein the fluorescent dye is included ata concentration of 1% or less by weight of the polycarbonate.
 28. Thearticle of claim 24, wherein the article is a bottle, having a bottomportion and a sealable top portion.
 29. The article of claim 28, whereinthe bottle has an integrally-molded handle.
 30. The article of claim 28,wherein the photoluminescent material is a fluorescent dye.
 31. Thearticle of claim 30, wherein the plastic is a polycarbonate.
 32. Thearticle of claim 31, wherein the fluorescent dye is selected from thegroup consisting of perylene derivatives, anthracene derivatives,indigoid and thioindigoid derivatives, imidazole derivatives,naphtalimide derivatives, xanthenes, thioxanthenes, coumarins,rhodamines, (2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene) andderivatives thereof.
 33. The article of claim 32, wherein thefluorescent dye included in the article is included at a concentrationof 1% or less by weight of the plastic.
 34. The article of claim 32,wherein the fluorescent dye in the article provides a blue or violetvisual effect and the fluorescent dye is included at a concentration of0.5 to 0.001% by weight.
 35. The article of claim 34, wherein thefluorescent dye in the article is included at a concentration of 0.3 to0.1% by weight.
 36. The article of claim 34, wherein the fluorescent dyein the article is included at a concentration of 0.1 to 0.005% byweight.
 37. The article of claim 32, wherein the fluorescent dye in thearticle provides a red, orange or green visual effect and thefluorescent dye is included at a concentration of less than 0.0005% byweight.
 38. The article of claim 37, wherein the fluorescent dye in thearticle is included at a concentration of 0.0001% to 0.0003% by weight.39. The article of claim 24, wherein the graphic images is formed fromcuts having a depth of from 0.5 to 3 mm or protrusions having a heightof from 0.5 to 5 mm or combinations thereof.
 40. The article of claim24, wherein the fluorescent dye has a quantum yield of 0.7 or greater.41. The article of claim 40, wherein the fluorescent dye has a quantumyield of 0.9 or greater.
 42. The article of claim 1, wherein the articlecomprises a flat or flattened disc or rectangular body having a majorsurface on which the graphic image is formed.
 43. The article of claim42, wherein the article is selected from the group consisting of keyfobs; one or more sides of a box, for example jewelry boxes or lunchboxes; panes for covering pictures; flat panels which can be used inchandeliers or wind chimes, office and desk accessories, including clipboards, CD cases, rulers, and trays; and window ornaments.
 44. Thearticle of claim 43, wherein the photoluminescent material is an organicfluorescent dye.
 45. The article of claim 44, wherein the plastic is apolycarbonate.
 46. The article of claim 45, wherein the fluorescent dyeis included at a concentration of 1% or less by weight of the plastic.47. The article of claim 46, wherein the fluorescent dye provides a blueor violet visual effect and the fluorescent dye is included at aconcentration of 0.5 to 0.001% by weight.
 48. The article of claim 47,wherein the fluorescent dye is included at a concentration of 0.3 to0.1% by weight.
 49. The article of claim 47, wherein the fluorescent dyeis included at a concentration of 0.1% to 0.005% by weight.
 50. Thearticle of claim 46, wherein the fluorescent dye provides a red, orangeor green visual effect and the fluorescent dye is included at aconcentration of less than 0.0005% by weight.
 51. The article of claim50, wherein the fluorescent dye is included at a concentration of0.0001% to 0.0003% by weight.
 52. The article of claim 45, wherein thefluorescent dye is selected from the group consisting of perylenederivatives, anthracene derivatives, indigoid and thioindigoidderivatives, imidazole derivatives, naphtalimide derivatives, xanthenes,thioxanthenes, coumarins, rhodamines,(2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene) and derivatives thereof.53. The article of claim 52, wherein the fluorescent dye is included ata concentration of 1% or less by weight of the plastic.
 54. The articleof claim 45, wherein the graphic images is formed from cuts having adepth of from 0.5 to 3,mm or protrusions having a height of from 0.5 to5 mm or combinations thereof.
 55. The article of claim 1, wherein thearticle has an irregular shape three dimensional shape with cuts orprotrusions formed in the surface thereof to produce a pattern ofluminescence that complements the three dimensional shape.
 56. Thearticle of claim 55, wherein the article is selected from the groupconsisting of jewelry, beads, buttons, toys, picture frames, eye glasseslenses, eye glass frames, pen barrels, telephones and telephone covers.57. The article of claim 55, wherein the photoluminescent material is afluorescent dye.
 58. The article of claim 57, wherein the plastic is apolycarbonate.
 59. The article of claim 58, wherein the fluorescent dyeis selected from the group consisting of perylene derivatives,anthracene derivatives, indigoid and thioindigoid derivatives, imidazolederivatives, naphtalimide derivatives, xanthenes, thioxanthenes,coumarins, rhodamines, (2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene)and derivatives thereof.
 60. The article of claim 59, wherein thefluorescent dye included in the article is included at a concentrationof 1% or less by weight of the plastic.
 61. The article of claim 59,wherein the fluorescent dye in the article provides a blue or violetvisual effect and the fluorescent dye is included at a concentration of0.5 to 0.001% by weight.
 62. The article of claim 59, wherein thefluorescent dye in the article provides a red, orange or green visualeffect and the fluorescent dye is included at a concentration of lessthan 0.0005% by weight.
 63. The article of claim 55, wherein the graphicimages is formed from cuts having a depth of from 0.5 to 3 mm orprotrusions having a height of from 0.5 to 5 mm or combinations thereof.64. The article of claim 1, wherein the photoluminescent material is anorganic nano-particle.
 65. The article of claim 64, wherein the organicnano-colorant comprises a dye selected from the group consisting ofperylene derivatives, anthracene derivatives, indigoid and thioindigoidderivatives, imidazole derivatives, naphtalimide derivatives, xanthenes,thioxanthenes, coumarins, rhodamines, or(2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene) and all theirderivatives.
 66. The article of claim 65, wherein the plastic ispolycarbonate.
 67. The article of claim 64, wherein the plastic ispolycarbonate.
 68. A method for making an article having a luminescentvisual effect in the form of a graphic image, comprising the step ofpreparing a molding composition comprising a plastic having an index ofrefraction of at least 1.4 and a photoluminescent material, molding thearticle from the molding composition, and forming cuts or protrusions,or both, in a surface of the molded article to define the graphic image,wherein the step of forming the cuts or protrusions can occur during orsubsequent to the molding step.
 69. The method of claim 68, wherein theplastic is a polycarbonate.
 70. The method of claim 69, wherein thephotoluminescent material is an organic fluorescent dye.
 71. The methodof claim 70 wherein the fluorescent dye is included at a concentrationof 1% or less by weight of the plastic.
 72. The method of claim 71,wherein the fluorescent dye is selected from the group consisting ofperylene derivatives, anthracene derivatives, indigoid and thioindigoidderivatives, imidazole derivatives, naphtalimide derivatives, xanthenes,thioxanthenes, coumarins, rhodamines,(2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene) and derivatives thereof.73. The method of claim 68, wherein the graphic images is formed fromcuts having a depth of from 0.5 to 3.0 or protrusions having a height offrom 0.5 to 5.0 or combinations thereof.
 74. The method of claim 68,wherein the photoluminescent material is an organic nano-particle. 75.The method of claim 74, wherein the organic nano-colorant comprises adye selected from the group consisting of perylene derivatives,anthracene derivatives, indigoid and thioindigoid derivatives, imidazolederivatives, naphtalimide derivatives, xanthenes, thioxanthenes,coumarins, rhodamines, or(2,5-bis[5-tert-butyl-2-benzoxazolyl]thiophene) and all theirderivatives.
 76. The method of claim 75, wherein the plastic ispolycarbonate.
 77. The method of claim 68, wherein the plastic ispolycarbonate.